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United States Patent |
5,756,075
|
Meyer
|
May 26, 1998
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Apparatus and method for sunless tanning
Abstract
Apparatus for simulating skin tanning comprises a receptacle containing a
fluid comprising dihydroxyacetone, a receptacle containing a fluid
comprising a primary amine, and dispensing means for simultaneously or
sequentially providing desired amount of dihydroxyacetone and amine.
Inventors:
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Meyer; Thomas A. (Germantown, TN)
|
Assignee:
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Schering-Plough HealthCare Products, Inc. (Memphis, TN)
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Appl. No.:
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712944 |
Filed:
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September 13, 1996 |
PCT Filed:
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March 25, 1993
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PCT NO:
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PCT/US93/02586
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371 Date:
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February 15, 1995
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102(e) Date:
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February 15, 1995
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PCT PUB.NO.:
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WO94/04130 |
PCT PUB. Date:
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March 3, 1994 |
Current U.S. Class: |
424/59; 424/60; 424/400; 424/401 |
Intern'l Class: |
A61K 007/42; A61K 007/44; A61K 007/00 |
Field of Search: |
424/59,60,63,400,401
|
References Cited
U.S. Patent Documents
2176923 | Oct., 1939 | Nitardy | 221/60.
|
2853423 | Sep., 1958 | La Via | 424/60.
|
2949403 | Aug., 1960 | Andreadis et al. | 424/59.
|
3177120 | Apr., 1965 | Black et al. | 167/90.
|
3290017 | Dec., 1966 | Davies et al. | 259/114.
|
3403207 | Sep., 1968 | Kreps et al. | 424/60.
|
3608709 | Sep., 1971 | Pike | 206/47.
|
3651931 | Mar., 1972 | Hsiung | 206/47.
|
3756389 | Sep., 1973 | Firth | 206/47.
|
3809224 | May., 1974 | Greenwood | 206/219.
|
3983994 | Oct., 1976 | Wyslotsky | 206/219.
|
4193989 | Mar., 1980 | Teng et al. | 424/60.
|
4434154 | Feb., 1984 | McShane | 424/60.
|
4458811 | Jul., 1984 | Wilkinson | 206/219.
|
4466805 | Aug., 1984 | Welters et al. | 8/406.
|
4496046 | Jan., 1985 | Stone et al. | 206/219.
|
4608043 | Aug., 1986 | Larkin | 604/87.
|
4609544 | Sep., 1986 | Herlihy | 424/59.
|
4772471 | Sep., 1988 | Vanlerberghe et al. | 424/450.
|
4968497 | Nov., 1990 | Wolfram et al. | 424/59.
|
Foreign Patent Documents |
424282 | Apr., 1991 | EP | 424/59.
|
425324 | May., 1991 | EP | 424/59.
|
1252400 | Dec., 1960 | FR | 424/59.
|
2062016 | May., 1981 | GB | 424/59.
|
2180215 | Mar., 1987 | GB | 424/59.
|
Other References
Chemical Abstracts, vol. 72, abstract 103635b.
Chemical Abstracts, vol. 95, abstract 30226g.
E. Wittgenstein and H. Berry, "Reaction of Dihydroxyacetone (DHA) with
Human Skin Callus and Amino Compounds", Journal of Investigative
Dermatology, vol. 36, pp. 283-285 (1961).
A. Meybeck, "A Spectroscopic Study of the Reaction Products of
Dihydroxyacetone with Aminoacids," Journal of the Society of Cosmetic
Chemists, vol. 28, pp. 25-35 (1977).
M.F. Bobin, M.C. Martini and J. Cotte, "Effects of Color Adjuvants on the
Tanning Effect of Dihydroxyacetone," Journal of the Society of Cosmetic
Chemists, vol. 35, pp. 265-272 (1984).
D. Debrovner, "Bottled Sunshine," American Druggist, Jul. 1992, pp. 42, 47
and 49.
"Sonnenschutzmittel und Braunungs-Gel," in Riechstoffe, Aromen,
Korperpflegemittel, vol. 28, No. 5, May 1970, p. 186.
|
Primary Examiner: Dodson; Shelley A.
Attorney, Agent or Firm: Franks; Robert A., Maitner; John J.
Parent Case Text
CROSS-REFERENCE TO RELATED APPLICATIONS
The present application is a continuation of Ser. No. 08/387,757 filed on
Feb. 15, 1995 and now abandoned, which itself is the United States
national application corresponding to International Application No.
PCT/US93/02586, filed Mar. 25, 1993, published as WO94/04130 Mar. 3, 1994
and designating the United States, which PCT application is in turn a
continuation of U.S. patent application Ser. No. 07/934,601 filed Aug. 24,
1992 and now abandoned, the benefit of which applications are claimed
pursuant to the provisions of 35 U.S.C. .sctn..sctn. 120, 363 and 365(C).
Claims
What is claimed is:
1. Apparatus for imparting artificial tan to skin, comprising:
(a) a receptacle containing a fluid formulation comprising
dihydroxyacetone;
(b) a receptacle containing a fluid formulation comprising a primary amine,
provided that the amine is not an .alpha.-amino acid; and
(c) dispensing means for simultaneously or sequentially providing desired
amounts of dihydroxyacetone and amine.
2. The apparatus of claim 1, wherein at least one of dihydroxyacetone and
amine is present in a solution.
3. The apparatus of claim 1, wherein at least one of dihydroxyacetone and
amine is present in an emulsion.
4. The apparatus of claim 1, wherein at least one of dihydroxyacetone and
amine is present in a gel.
5. The apparatus of claim 1, wherein the dispensing means provides molar
ratios of dihydroxyacetone to amine about 0.5 to about 10.
6. The apparatus of claim 5, wherein there are provided molar ratios of
dihydroxyacetone to amine about 1 to about 5.
7. The apparatus of claim 5, wherein there are provided molar ratios of
dihydroxyacetone to amine about 1 to about 3.
8. The apparatus of claim 1 wherein at least one formulation establishes pH
values about 3 to about 13, when desired amounts of the formulations are
mixed.
9. The apparatus of claim 8, wherein pH values about 7 to about 11 are
established.
10. The apparatus of claim 8, wherein pH values about 9 to about 10 are
established.
11. The apparatus of claim 1, wherein the amine has the formula RNH.sub.2,
in which R is selected from the group consisting of:
--(CH.sub.2).sub.n COOH;
--(CH.sub.2).sub.x COOR';
--(CH.sub.2).sub.y CH.sub.3 ;
--(CH.sub.2).sub.x OH;
--CH.sub.2 (C.sub.6 H.sub.5);
--C(O)(C.sub.6 H.sub.5);
--(CH.sub.2).sub.x CH(OR').sub.2 ;
--(CH.sub.2).sub.x OR';
--(OCH.sub.2 CH.sub.2).sub.z NH.sub.2 ;
cyclic groups containing N, O or S in the ring;
--Si(OH).sub.3 ; and
--Si(OR').sub.3 ;
wherein n is an integer of at least 2, x is an integer of up to 22, y is an
integer of 5 to about 22, z is an integer of up to about 10, and R' is an
alkyl group having up to about 10 carbon atoms.
12. A method for imparting artificial tan to human skin, comprising
contacting the skin with dihydroxyacetone and a primary amine having the
formula RNH.sub.2, wherein R is selected from the group consisting of:
--(CH.sub.2).sub.n COOH;
--(CH.sub.2).sub.x COOR';
--(CH.sub.2).sub.y CH.sub.3 ;
--(CH.sub.2).sub.x OH;
--CH.sub.2 (C.sub.6 H.sub.5);
--C(O)(C.sub.6 H.sub.5);
--(CH.sub.2).sub.x CH(OR').sub.2 ;
--(CH.sub.2).sub.x OR';
--(OCH.sub.2 CH.sub.2).sub.z NH.sub.2 ;
cyclic groups containing N, O or S in the ring;
--Si(OH).sub.3 ; and
--Si(OR').sub.3 ;
wherein n is an integer of at least 2, x is an integer of up to 22, y is an
integer of 5 to about 22, z is an integer of up to about 10, and R' is an
alkyl group having up to about 10 carbon atoms.
13. The method of claim 12, wherein the dihydroxyacetone and amine are
applied to skin sequentially.
14. The method of claim 12, wherein the dihydroxyacetone and amine are
applied to skin substantially simultaneously.
15. The method of claim 12, wherein a formulation containing
dihydroxyacetone and amine is applied to skin.
16. The method of claim 12, wherein pH values between about 3 and about 13
are established as skin is initially contacted.
17. The method of claim 16, wherein pH values between about 7 and about 11
are established.
18. The method of claim 16, wherein pH values between about 9 and about 10
are established.
19. The method of claim 12, wherein the molar ratio of dihydroxyacetone to
amine is about 0.5 to about 10.
20. The method of claim 12, wherein the molar ratio of dihydroxyacetone to
amine is about 1 to about 5.
21. The method of claim 12, wherein the molar ratio of dihydroxyacetone to
amine is about 1 to about 3.
22. A composition for immediate application to skin, comprising a mixture
of:
(a) a formulation containing dihydroxyacetone; and
(b) a formulation containing a primary amine having the formula RNH.sub.2,
wherein R is selected from the group consisting of:
--(CH.sub.2).sub.n COOH;
--(CH.sub.2).sub.x COOR';
--(CH.sub.2).sub.y CH.sub.3 ;
--(CH.sub.2).sub.x OH;
--CH.sub.2 (C.sub.6 H.sub.5);
--C(O)(C.sub.6 H.sub.5);
--(CH.sub.2).sub.x CH(OR').sub.2 ;
--(CH.sub.2).sub.x OR';
--(OCH.sub.2 CH.sub.2).sub.z NH.sub.2 ;
cyclic groups containing N, O or S in the ring;
--Si(OH).sub.3 ; and
--Si(OR').sub.3 ;
wherein n is an integer of at least 2, x is an integer of up to 22, y is an
integer of 5 to about 22, z is an integer of up to about 10, and R' is an
alkyl group having up to about 10 carbon atoms.
Description
FIELD OF THE INVENTION
This invention relates to apparatus which is useful in the simulated
tanning of skin. More particularly, the invention relates to apparatus
which is used in the treatment of skin with dihydroxyacetone compositions,
to form a brownish coloration thereon.
INTRODUCTION TO THE INVENTION
It has long been known that certain compounds form pigments when applied to
the skin. Products containing dihydroxyacetone (frequently simply
abbreviated to "DHA") have been marketed since the early 1960's, and have
been found satisfactory by many persons who wish to give their skin the
appearance of an attractive tan, but do not desire to risk the now
well-appreciated health hazards of exposure to solar or
artificially-generated ultraviolet radiation.
However, some persons have not obtained the desired results from DHA
applications. A small number of individuals develop a coloration which
tends to appear yellowish or orange. Some others, probably due to
perspiration, rubbing or washing during the slow generation of color as
skin components react with DHA, or to a lack of care to evenly apply the
DHA, develop uneven coloration.
The chemistry of DHA-skin interaction has been investigated by several
workers. Wittgenstein and Berry published a paper "Reaction of
Dihydroxyacetone (DHA) with Human Skin Callus and Amino Compounds," in The
Journal of Investigative Dermatology, Vol. 36, pages 283-286 (1961),
describing work to characterize the browning phenomenon. They reported
that DHA reacts with a number of compounds, including ammonia and amino
acids, to form a brown color, and theorized that skin browning is due to
the reaction of DHA with free amino groups in the skin, the amino groups
probably being on arginine molecules which are present in skin proteins.
A. Meybeck published "A Spectroscopic Study of the Reaction Products of
Dihydroxyacetone with Aminoacids" in Journal of the Society of Cosmetic
Chemists, Vol. 28, pages 25-35 (1977), and characterized brown pigments
formed from the reaction of DHA with amino and other acids at 100.degree.
C. Further experiments at 37.degree. C. were conducted to better simulate
reactions which may occur in the skin: DHA was reacted with the amino
acids glycine, lysine, alanine, serine and arginine, but only glycine and
lysine produced significant amounts of pigment after 24 hours. It was
concluded that DHA must act by initially condensing with free amino acids
at the skin surface, followed by polymerization and linking to proteins in
the stratum corneum, probably through lysine side chains.
A further study was reported by M. F. Bobin, M. C. Martini and J. Cotte,
"Effects of Color Adjuvants on the Tanning Effect of Dihydroxyacetone,"
Journal of the Society of Cosmetic Chemists, Vol. 35, pages 265-272
(1984). This work involved measuring the rate of color development after
mixing DHA and various amino acids or their derivatives, and applications
of DHA and methionine sulfoxide in vivo. It was concluded that methionine
sulfoxide is a useful adjuvant to DHA, as the combination provided rapid
color development, plus a more intense and long lasting color than would
be obtained with only DHA. This result was thought to result from the
affinity of methionine sulfoxide for keratin.
Chemical Abstracts, Vol. 95, abstract 30226g (1981) summarizes a German
patent document (3,037,497) pertaining to dyeing skin, hair, feathers,
fur, etc. by treating with a mixture of DHA and an amino acid sulfoxide.
When DHA and methionine sulfoxide were applied in cream formulations, skin
turned a deep brown color after three hours and the color was more
resistant to washing than that obtained with only DHA.
Black et al., in U.S. Pat. No. 3,177,120, discussed the problem of
including DHA and amino group-containing sunscreens together in a
formulation, and concluded that only sunscreens free from amino groups
should be used, to prevent formation of a yellow or brown color in the
storage container; color formation is also said to be accompanied by
inactivation of both the DHA and sunscreen.
In spite of the teachings in the art relating to the use of DHA with
.alpha.-amino acids and their derivatives, it has been found that color
formed thereby does not have a desired substantivity, or resistance to
removal by rubbing or washing. Thus, it is desired to provide apparatus
and a method for browning skin to form simulated tans having improved
substantivity and colors which closely resemble those obtained from
exposure to ultraviolet radiation.
SUMMARY OF THE INVENTION
The invention, in one aspect, provides an apparatus for imparting
artificial tan to skin, comprising: a receptacle containing a fluid
formulation comprising dihydroxyacetone; a receptacle containing a fluid
formulation comprising a primary amine; and dispensing means for
simultaneously or sequentially providing desired amounts of
dihydroxyacetone and amine. The invention also includes a method for
imparting artificial tan to skin, comprising simultaneously or
sequentially contacting the skin with dihydroxyacetone and a primary
amine. Also included is a composition for immediate application to skin,
comprising dihydroxyacetone, at least one primary amine and a suitable
carrier.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a cross-sectional view of a pouch container having two
compartments.
FIG. 2 is a cross-sectional view of a squeeze bottle having two
compartments.
FIG. 3 is a cross-sectional view of a dual-compartment tube container.
FIG. 4 is a cross-sectional view of a container having two compartments and
a dual pump dispenser.
FIG. 5 is a cross-sectional view of a dual-compartment pressurized
dispensing container.
DETAILED DESCRIPTION OF THE INVENTION
The invention will be described with reference to the accompanying
drawings. In the description and claims, all percentages are expressed on
a weight basis, unless otherwise noted.
In accordance with the invention, there is provided apparatus for imparting
a simulated tan to skin, the apparatus having separate compartments for a
formulation containing dihydroxyacetone and a formulation containing a
primary amine. As previously noted, it is important to prevent the mixing
of the components until a user is ready to make a skin application, to
prevent premature reaction and color formation. The apparatus can be
configured to simultaneously dispense the formulations, in desired
amounts, or to sequentially dispense them. If sequentially dispensed, the
formulations can be mixed before spreading onto the skin, or can be spread
in the order of dispensing.
Referring to FIG. 1, there are shown the features of a two-compartment
pouch 10. Included is septum 12 which, in the least complex embodiment
where the pouch comprises heat sealed layers of a thermoplastic substance,
is merely a heat sealed seam to divide the volume of the pouch. This
septum divides the volume into chambers 14 and 16. Tearing notch 18 can be
provided to facilitate removal of the top of the pouch, when it is desired
to dispense formulations contained therein. This embodiment will be used
primarily for single-use quantities, the pouch holding an appropriate
quantity for application once to the whole body or a portion thereof, such
as only the face.
As an alternative to a tearing notch, the user can simply cut off the top
of the pouch with scissors or a knife. Further, rather than dispensing the
two formulations from the pouch in two streams, as would be done with the
configuration depicted, septum 12 can be made frangible; applying pressure
with the fingers to one side of the pouch will rupture the septum and
permit mixing of the formulations by sequentially applying pressure to the
two sides, after which a single composition containing both DHA and amine
can be applied. Of course, such mixing should only be conducted
immediately before use.
For sequential application of the two formulations, another tearing notch
(not shown) can be provided on the opposite side of the pouch from notch
18, and the septum can be extended to the uppermost limit of the pouch.
This will permit only one compartment to be opened by pulling above a
notch.
FIG. 2 is a view of a squeeze bottle 20, which is provided with septum 22
to form two compartments 24 and 26. The bottle is conveniently formed by
molding with thermoplastic substances, as is well known in the art. In a
typical embodiment, threads 34 will be provided for closure with a
conventional screw cap (not shown). The threads will not be needed if the
bottle is closed by alternative means, such as a pressed on flip cap.
Preferably, gripping indentations 28 are provided, to ensure that the
bottle is squeezed in locations which will apply approximately uniform
pressure to the two compartments, i.e., not to a less deformable area such
as that directly over the septum. Upon pressure application, formulations
are dispensed from the compartments through orifices 30 and 32.
The bottle can be used for sequential applications of DHA and amine, by
providing separate closures for the two orifices. As an example,
individual snap caps can be provided over the orifices. The user would be
required to dispense an appropriate amount of a component, rub that
component into the skin and, immediately or after a prescribed time, apply
the second component to the skin in a similar manner. Application of equal
amounts of the components can be accomplished with sufficient accuracy by
noting the lengths of dispensed fluids on the skin; the bottle can be
provided with length scales marked thereon to make this more convenient.
Referring now to FIG. 3, there is shown a cross-sectional view of a
collapsible tube assembly 36 which is useful in the invention. As shown,
the outer tube 38 surrounds the inner tube 40, and contents of the outer
and inner tubes can be discharged through outlets 42 and 44, respectively,
by squeezing the assembly. A threaded area 46 is provided for attachment
of a closure (not shown). Any desired number of outlets can be provided
for the tubes and any desired type of closure can be used, the invention
not being restricted to a threaded cap.
The assembly can be fabricated from any materials normally utilized for
tubes dispensing medications, cosmetic materials, hygiene products such as
toothpastes, cleaning compositions and the like, subject to the usual
requirement that the materials of construction do not react with
formulations contained therein to an appreciable extent during at least
the expected storage term. Frequently used materials include metals,
polymers and composites, including laminates. Typically, the assembly will
be closed at its bottom end by crimping or heat sealing, depending upon
the materials of construction. To assure that formulations are dispensed
in predetermined relative amounts from the outer and inner tubes, means
(not shown) such as a key can be provided at the bottom of the assembly
for uniformly collapsing the tubes; as the bottom of the assembly is wound
around a rotated key, approximately the same pressure will be applied to
the two tubes.
A further apparatus is shown in cross-section as FIG. 4. In this figure,
dispensing container 48 comprises bottle 50, having dividing septum 52
which forms two compartments 54 having any desired geometry. Cap 56 is
adapted to fit over the outlets of pumps 58, mounted to close the
compartments and which can be any of the well-known spring loaded check
valve pumps such as are used with hand lotions and other cosmetic
products. Pressing down on the cap causes formulations to be
simultaneously dispensed from conduits 62; releasing the cap permits it to
rise under pressure from springs in the pumps, simultaneously reloading
the pumps with stored formulations through dip tubes 60.
This apparatus requires no particular care on the part of the user to
obtain a correct ratio of the formulations, in cases where the
formulations are to be simultaneously dispensed and applied, but permits
complete separation of the components until dispensing. By providing
separate caps over the pumps, it would be possible to dispense the
formulations at different times, should this be desired. In either
embodiment, reproducible amounts will be dispensed simply by pressing the
cap down for its full length of travel each time, without any need for a
user to make measurements.
FIG. 5 relates to a pressurized aerosol container which can be used to
dispense two components simultaneously. Container 64 comprises external
shell 66, with bottom closure 68 attached; preferably, both of these
components will be fabricated from metals, with the bottom closure crimped
or welded to the shell. Gas filling port 70 is provided to seal the
container after a pressurizing gas is introduced.
The container is divided by barrier 72, which is provided with one or more
perforations 74 near the bottom of the container, to equalize gas pressure
in the two sections formed by the barrier. Each section has an
accordion-pleated bag 76, preferably fabricated from a plastic material,
to contain a formulation, the bags each being connected to an aerosol
valve 78 which is actuated to release formulation by its depression into
the container. Cap 80 is utilized to simultaneously depress the valves,
and directs formulations through conduits 82 for application to a desired
area.
This apparatus has the advantages of dispensing desired relative amounts of
the contained formulations without any special care on the part of the
user, and being very simple to use. By using plastic bags to contain the
formulations, the aerosol container needs not be chemically compatible
with the formulations, and the propellant will not normally be in contact
with the formulations. Of course, costs can be reduced by changing the
design to make use of sealed compartments having pistons driven by gas
pressure to force formulations out through the valves, but piston sealing,
compatibility of construction materials with the formulations and other
considerations will complicate the product design. Many alternatives will
be apparent to those skilled in aerosol container packaging.
Another useful package for the present invention has two compartments,
divided by a removable or frangible barrier. An example is the collapsible
tube of U.S. Pat. No. 2,176,923 to Nitardy, where two substances are
separated in a tube by a transverse partition which is a collapsible disk
having a central aperture; expressible plugs in the aperture are removed
by applying pressure to the bottom of the tube, causing the substances to
mix. U.S. Pat. No. 3,290,017 to Davies et al. is related, having a disc
which can be moved from a barrier position to a mixing position in a tube
by external finger pressure.
A further example is found in U.S. Pat. No. 3,608,709 to Pike, where a
multiple-compartment laminated pouch is described. This pouch, when
external pressure is applied, will form a single compartment by breakage
of the internal barrier, permitting two formulations contained therein to
mix. Other packages having frangible internal barriers are shown in the
following U.S. Pat. Nos. 3,756,389; 4,458,811; and 4,608,043; these can be
adapted for use in the present invention.
U.S. Pat. No. 3,809,224 to Greenwood shows another useful package, having
an external clamp divider seal which can be removed to permit mixing of
components stored separately when the clamp is in place.
Each of these packages having a frangible or removable barrier will be
suitable for single use unit packaging only, since it will be necessary to
use the entire contents of the package promptly after the DHA and amine
formulations are mixed, due to the previously discussed reaction.
The foregoing is a description of representative packaging techniques for
maintaining and dispensing a formulation comprising dihydroxyacetone and a
formulation comprising a primary amine. Both formulations must be fluid,
that is, capable of flow under the influence of gravity or a moderate
externally applied pressure. Examples of useful fluid formulations are
ointments, dispersions such as creams and lotions, gels, solutions, and
the like, each of which (and preparative techniques therefor) are very
well known to those skilled in the formulating art.
Typically, both formulations which are to be used together will be of the
same type, e.g., if one is a gel, the other also will be a gel to
facilitate application and mixing. However, it is not always necessary to
observe this general principle.
Amines which are useful in preparing the formulations of the invention have
the general formula RNH.sub.2, where R is selected from the group
consisting of:
--(CH.sub.2).sub.n COOH;
--(CH.sub.2).sub.x COOR';
--(CH.sub.2).sub.y CH.sub.3 ;
--(CH.sub.2).sub.x OH;
--CH.sub.2 (C.sub.6 H.sub.5);
--C(O)(C.sub.6 H.sub.5);
--(CH.sub.2).sub.x CH(OR').sub.2 ;
--(CH.sub.2).sub.x OR';
--(OCH.sub.2 CH.sub.2).sub.z NH.sub.2 ;
cyclic groups containing N, O or S in the ring;
--Si(OH).sub.3 ; and
--Si(OR').sub.3 ;
wherein n is an integer of at least 2, x is an integer of up to 22, y is an
integer of 5 to about 22, z is an integer of up to about 10, and R' is an
alkyl group having up to about 10 carbon atoms. The term "alkyl," is used
herein to refer to substituted or unsubstituted groups, branched or
unbranched, permissible substituents being halogens, nitrogen-containing
groups, sulfur-containing groups, hydroxy groups, carbonyl-containing
groups, and the like. In general, the amount of heteroatom substitution in
an alkyl group will be less than one such atom per each five carbon atoms
in the group and, usually, the alkyl groups will be hydrocarbon groups.
Where "CH.sub.2 " appears in the groups listed as possibilities for R,
above, these CH.sub.2 units may be substituted similarly to the alkyl
groups. It should be noted that more than one amino group can be present
in a compound; amino groups are not considered to be
"heteroatom-containing" for purposes of this invention.
Cyclic groups having N, O or S in the ring include those based upon
aziridine, azetidine, pyrrolidine, pyrrole, piperidine, diazole,
imidazole, tetrazole, oxole, oxolane, thiole, thiazole and the like. In
particular, amines having an oxole or oxolane group have been found useful
in the invention.
Volumes and active ingredient concentrations of dispensed formulations
should be chosen to provide molar ratios of DHA to amine about 0.5 to
about 10. More preferably, the ratios should be about 1 to about 5. Still
more preferred are molar ratios about 1 to about 3. If the number of moles
of DHA exceed the number of moles of amine, a portion of the DHA will
remain free to react with amino groups in the skin, increasing the
substantivity of the color formed; thus, a molar excess of DHA is
preferred. Although the rate of color formation in the skin (with free
amino groups present there) is considerably slower than that of DHA with
provided primary amine on or near the skin surface, color formed in the
skin is more resistant to removal by washing and abrasion. For this
reason, it is preferable to establish both the early and frequently more
intense color on the skin surface, and the more permanent but slower
forming color in the skin layers.
It has been found that pH at the time of application affects the resulting
color. In general, either the DHA formulation or the amine formulation
should be able to establish pH values about 3 to about 13 locally when
applied to the skin. More preferred are values about 7 to about 11, with
values about 9 to about 10 being particularly preferred with some
formulations. The optimal pH for a given amine application will be
somewhat dependent upon the pK.sub.a of that amine, and can be determined
by applying formulations having different pH values to the skin. For
n-Dodecylamine, having a pK.sub.a of 10.63, a more reddish hue forms when
the pH is much lower than 9 or 10, while a more yellowish hue forms at
much higher pH values.
To compare simulated tans created by different means, it is helpful to have
an objective, instrumental measurement of colors and intensities.
Accordingly, a method has been developed using a Minolta Chroma Meter
CR-200, which uses reflected light from a surface and gives results in
terms of the CIE (International Commission on Illumination) tristimulus
values. These values are subsequently transformed mathematically into the
L* a* b* color space, wherein the magnitudes of changes in hue and
intensity of color correspond closely with those percieved by the human
eye.
L*, being achromatic, ranges from black (L*=0) to white (L*=100); this term
is called "metric lightness" and is a measure of how light or dark a color
is, relative to a matching shade of gray. Hue is measured in terms of the
chromaticity coordinates a* and b*, where a* indicates redness (a*>0) and
b* indicates yellowness (b*>0). The values of a* and b* can be plotted
with a* as the x-axis and b* as the y axis, to give quantitative color
information: "metric chroma" is the length of a line from the origin
(a*=0, b*=0) to the point of a sample reading, while "metric hue angle" is
the angle between the a* axis and the metric chroma line. Metric chroma
indicates the strength of a color response (i.e., the extent to which a
color differs from its matching shade of gray). Metric hue angle
quantifies hue in degrees, with larger values indicating more yellow hues
and smaller values indicating more red (or less yellow) hues.
The meter is used to measure natural tans with a number of subjects, to
establish a target for the appearance of tans produced by DHA reactions.
In general, it is found that points on a chromaticity plot for dark tans
will have b* from about 19 to about 24, with a* ranging from about 10 to
about 14. For medium tans, b* will be about 20 to about 24, with a* from
about 9 to about 12. For light tans, b* will be about 18 to about 20, with
a* about 7 to about 10. Rather than being a point, the target color is
represented by the area on the plot where natural tans lie. Values of
metric chroma increase steadily as tans progress from light to medium, but
increase much more slowly as tans become more dark than "medium." In
contrast, values of metric hue angle overlap significantly for light,
medium and dark tans, except for very dark tans which have increased
redness (decreased metric hue angle).
Metric lightness is the third required parameter for characterizing natural
tans. L* values decrease as tans become darker, a difference of about one
unit being discernable to a trained observer. For natural tans, L* ranges
from about 47 to about 53 for dark tans, about 54 to about 57 for medium
tans and about 58 to about 64 for light tans.
The meter is also used to measure the characteristics of simulated tans
obtained using only DHA applications. Several subjects are treated with an
oil in water emulsion containing 5 percent DHA, with applications (2 mg
DHA/cm.sup.2) being made once each day for four days. After the first day,
values for b* are about 13 to about 21, the a* values are about 3 to about
8 and L* values are about 63 to about 74. After two days, b* is about 15
to about 23, a* is about 5 to about 8 and L* is about 62 to about 72.
After the third day, b* is about 16 to about 23, a* is about 5 to about 9
and L* is about 61 to about 71. After four days, b* is about 17 to about
24, a* is about 5 to about 9 and L* is about 61 to about 70. The hues for
all but a few of the readings are more yellowish than the tan target area,
and all but a few of the readings indicate tans more light than natural
tans, even though comparable levels of metric chroma are generated. It can
generally be stated that simulated tans using only DHA are more yellow and
lighter than natural tans having similar extents of color formation.
The following examples are provided to illustrate various aspects of the
invention, and are not to be construed as limiting the invention in any
manner.
EXAMPLE 1
A gel containing 5 percent n-Dodecylamine is prepared, using the following
components:
______________________________________
70.5 grams Alcohol SD40-2
5 grams Dodecylamine
20 grams Water
1.5 grams Hydroxypropylcellulose
3 grams Hydrochloric acid, 6N
______________________________________
The gel is prepared by dissolving the amine in the alcohol, slowly adding
the water, with stirring, to obtain a clear solution, adding the
hydroxypropylcellulose with mixing, continuing mixing until the mixture is
free of lumps, and adding the hydrochloric acid to obtain pH values of 9
to 9.5.
The hydroxypropylcellulose is sold as Klucel HF.TM. by Hercules Inc.,
Wilmington, Del. U.S.A.
EXAMPLE 2
A gel containing 10 percent n-Dodecylamine is prepared, using the procedure
and components of the preceding example, and the following amounts:
______________________________________
70.0 grams Alcohol SD40-2
10.0 grams Dodecylamine
11.5 grams Water
1.5 grams Hydroxypropylcellulose
7.0 grams Hydrochloric acid, 6N
______________________________________
EXAMPLE 3
A gel containing 10 percent n-Dodecylamine is prepared with remaining
ingredients as in the preceding example, but using 14 grams of water and
4.5 grams of hydrochloric acid. This gel has a pH about 10.
EXAMPLE 4
A gel is prepared from the following components:
______________________________________
Part Grams Component
______________________________________
A 65.45 Water
1.44 Polyquarternium-10
B 19.16 Alcohol SD40-2
C 0.17 Water
0.02 Citric acid
D 4.78 Water
7.10 Dihydroxyacetone
0.10 d,1-Panthenol
0.05 Aloe concentrate
E 1.44 Polysorbate-80
0.29 Fragrance
______________________________________
The gel, containing 7.10 percent DHA, is prepared by adding the
Polyquarternium-10 to the water of part A, with stirring until the mixture
is thick (about one hour). The alcohol of part B is added slowly, with
stirring, to the part A mixture to form a uniform gel. Citric acid is
dissolved in the water of part C, then mixed into the gel. The part D
ingredients are dissolved in the water of that part, then mixed into the
gel. Finally, the fragrance and Polysorbate-80 are mixed, and combined
with the gel.
To 50 grams of the foregoing gel are added 21 grams of 50 percent (in
water) Alcohol SD40-2, to prepare a gel containing 5 percent DHA.
The polyquaternium-10 is available from Amerchol Corporation, Edison, N.J.
U.S.A. as Ucare Polymer JR-30M.TM.. The polysorbate-80 is sold by ICI
Americas Inc., Wilmington, Del. U.S.A. as Tween 80.TM..
EXAMPLE 5
A gel containing 10 percent DHA is prepared using the following components:
______________________________________
Part Grams Component
______________________________________
A 53.30 Water
1.50 Polyquaternium-10
B 20.00 Alcohol SD40-2
C 0.18 Water
0.02 Citric acid
D 15.00 Water
10.00 Dihydroxyacetone
______________________________________
The polymer of part A is slowly added, with constant stirring, to the water
of that part; mixing is continued until the mixture is thick. Alcohol of
part B is slowly mixed into the thick mixture. Citric acid is dissolved in
the water of part C and stirred into the mixture. Finally, the DHA is
dissolved in the water of part D and combined with the mixture. The
polyquaternium 10 can be obtained from Amerchol Corporation as Ucare
Polymer JR-30M.TM..
EXAMPLE 6
A lotion is prepared using the following components:
______________________________________
Part Grams Component
______________________________________
A 61.32 Water
B 10.00 Emulsifying wax
C 10.00 n-Dodecylamine
10.00 Propylene glycol
D 7.28 Water
1.40 Citric acid
______________________________________
The water of part A is heated to 70.degree. C., and the wax of part B is
heated to 70.degree. C. The heated components are combined, with rapid
mixing, and cooled to 45.degree. C. with mixing. The dodecylamine is
heated to liquefaction and mixed into the propylene glycol, then the
mixture is combined with the previous components. The combination is
cooled to 35.degree. C. The citric acid of part D is dissolved in the
water of that part, and the solution is added to the preceding components,
to adjust the pH of the composition to about 9.0 to 9.5.
The emulsifying wax is sold as Polawax.TM. by Croda Inc., New York, N.Y.
U.S.A.
EXAMPLE 7
A lotion is prepared, using the following components:
______________________________________
Part Grams Component
______________________________________
A 62.00 Water
B 15.00 Emulsifying wax
1.00 n-Hexadecyl alcohol
2.00 Polyoxyethylene(10)oleyl ether
C 10.00 n-Dodecylamine
D 1.75 Citric acid
5.00 Water
E 3.25 Water
______________________________________
The water of part A is heated to 70.degree. C. The components of part B are
combined, heated to 70.degree. C., and the dodecylamine is added. All
preceding components are combined, with vigorous mixing, and cooled to
45.degree. C. The citric acid is dissolved in the water of part D and
added to the preceding components, to obtain a pH about 9. The water of
part E is then combined with the other components.
The emulsifying wax is Polawax.TM., sold by Croda Inc. The
polyoxyethylene(10)oleyl ether is sold by ICI Americas Inc., Wilmington,
Del. U.S.A. as Brij 97.TM..
EXAMPLE 8
A lotion is prepared, using the following components:
______________________________________
Part Grams Component
______________________________________
A 60.20 Water
1.18 Polyoxyethylene(10)cetyl ether
B 6.50 Polyoxyethylene fatty alcohol
ethers
0.82 Polyoxyethylene(2)cetyl ether
0.30 n-Hexadecyl alcohol
5.00 Isopropyl palmitate
C 15.00 Water
10.00 Dihydroxyacetone
D 1.00 Biocide
______________________________________
The part A components are mixed and heated to about 75.degree. C. The part
B components are mixed and heated to about 75.degree. C. to form a
solution. Parts A and B components are combined with vigorous mixing, then
cooled to about 50.degree. C. The DHA is dissolved in the water of part C,
and combined with preceding components. Finally, the biocide is mixed into
the preparation.
The polyoxyethylene(10)cetyl ether and polyoxyethylene(2)cetyl ether are
sold by ICI Americas Inc., Wilmington, Del. U.S.A. as Brij 56.TM. and Brij
52.TM., respectively. The polyoxyethylene fatty alcohol ethers are sold by
Amerchol Corp., Edison, N.J. U.S.A. as Promulgen G.TM..
EXAMPLE 9
A lotion is prepared, as in the preceding example, except that 65.2 grams
of water are used in part A and the isopropyl palmitate is omitted.
EXAMPLE 10
An alcoholic solution is prepared by mixing 70 milliliters of SD-40 alcohol
with 10 grams of n-Dodecylamine, adjusting the pH to 9.0 with concentrated
hydrochloric acid, then adjusting the volume to 100 milliliters with
additional alcohol.
EXAMPLE 11
An alcoholic solution is prepared by dissolving 10 grams of
Dihydroxyacetone in 50 milliliters of water, and diluting to 100
milliliters with SD-40 alcohol.
EXAMPLE 12
The color formed by treating skin (5 cm.times.5 cm) with 25 microliters of
an amine formulation and 25 microliters of a DHA formulation is studied.
In each test, the first applied formulation is well rubbed into the skin,
then the second is promptly rubbed into the skin. In each test, skin which
is originally measured to be outside the tanning target area acquires a
color within the target area and with appropriate values of L*, when
measured four hours after application of the formulations.
The following combinations of formulations from preceding examples are
tested:
______________________________________
Amine, Example No.
DHA, Example No.
______________________________________
1 4
2 5
3 5
6 5
6 8
6 9
7 8
7 9
10 11
______________________________________
EXAMPLE 13
Tests are conducted to determine the relative substantivity of color formed
by the use of DHA and amine formulations of preceding examples.
Substantivity is determined by measurement of color before and after a
10.times.8 centimeter, 500-gram block, fitted with a towel covering its
lower surface, is pulled across the skin through five cycles, using a
back-and-forth motion. This test is conducted both with the towel dry, and
saturated with water.
In all cases, DHA and amine formulations are applied to skin immediately
after readings are taken with the Minolta Chroma Meter, using 25
microliters of each formulation on a 25 cm.sup.2 skin area. A period of
seven hours is allowed for color development, then readings are again
taken; the difference in total color is termed "Initial .DELTA.E" for the
tables which follow. After each of dry and wet rubbing, measurements are
made and .DELTA.E is again determined. Thus, .DELTA.E always represents
total color difference between treated and untreated skin. The following
equation is used to calculate .DELTA.E:
›(L*.sub.u -L*.sub.T).sup.2 +(a*.sub.u -a*.sub.T).sup.2 +(b*.sub.u
-b*.sub.T).sup.2 !.sup.1/2
where the subscripts "U" represent readings with untreated skin and the
subscripts "T" represent readings with treated skin.
Results are as shown below, indicating that: (1) about two to three times
more total color is formed after seven hours when both amine and DHA are
applied, as compared to only DHA applications; and (2) the presence of
amine improves resistance to both dry and wet rubbing. All results are
averages for four subjects. Visually, differences in .DELTA.E amounting to
at least about 0.5 can be discerned by a trained observer.
______________________________________
Amine DHA .DELTA.E
No. No. Initial Dry Wet
______________________________________
7 9 8.9 .+-. 1.5 8.5 .+-. 1.6
6.4 .+-. 1.0
2 5 10.8 .+-. 1.5
9.8 .+-. 1.3
7.6 .+-. 1.3
10 11 10.4 .+-. 1.9
9.7 .+-. 1.7
6.4 .+-. 1.2
-- 9 5.7 .+-. 1.3 5.0 .+-. 1.2
4.9 .+-. 1.3
-- 5 5.2 .+-. 1.2 4.9 .+-. 1.4
4.6 .+-. 1.2
-- 11 4.1 .+-. 1.0 3.8 .+-. 0.9
3.4 .+-. 0.7
______________________________________
EXAMPLE 14
Substantivity to water rinsing indicates the water solubility of the color
formed. A suitable test involves measuring skin color, applying
formulations to the skin, allowing color to develop for about six hours,
then repeating the color intensity measurement. A gentle stream of
luke-warm tap water is allowed to flow over the treated skin for two
minutes, then the skin is dried by gently patting with dry paper towels,
taking care to not rub the skin. A final skin color measurement is then
taken, thirty minutes later. Values of .DELTA.E can be calculated, as in
the preceding example.
The following results are obtained with various amines plus DHA, as
compared with DHA only. The amine "MAD" is n-Dodecylamine, formulated as
in preceding Example 2. Glycine is used as an aqueous solution containing
4.1 percent of the amino acid, and adjusted to pH 9.0 with hydrochloric
acid. The n-Butylamine is a 2.1 percent solution in 50 percent by volume
ethanol, 50 percent by volume water, adjusted to pH 9.0. The n-Octylamine
is a 3.5 percent solution in a similar 50 volume percent ethanol, adjusted
to pH 9.1. Cetyl amine is 6.6 percent n-Hexadecylamine in ethanol,
adjusted to pH 9.3. The DHA is formulated according to preceding Example
5, for the glycine and MAD tests (25 microliters of each formulation
applied to 25 cm.sup.2 of skin), and according to preceding Example 4 for
the butyl, octyl and cetyl amine tests (10 microliters of each formulation
applied to 6.25 cm.sup.2 of skin).
In the results, "% Color Remaining" is calculated by the equation
(.DELTA.E.sub.RINSED /.DELTA.E.sub.UNRINSED .times.100) for the
application of both amine and DHA formulations, while "Color Increase" is
calculated from (.DELTA.E.sub.RINSED /.DELTA.E.sub.DHA-UNRINSED),
representing the color increase over unrinsed applications of only DHA.
______________________________________
% Color Color
Amine Subject Remaining
Increase
______________________________________
MAD 1 97 2.1
2 100 3.9
3 88 1.8
Glycine 1 55 .78
2 64 .88
Butyl 1 49 .73
Octyl 1 90 1.7
Cetyl 1 72 1.9
______________________________________
EXAMPLE 15
A test similar to that of the preceding example is conducted to compare the
substantivity of an aliphatic amine and two .alpha.-amino acids. A 1.11
molar DHA formulation as in preceding Example 5 is used, together with one
of the following formulations: 0.54 molar lysine in 50 percent by volume
aqueous ethanol, adjusted to pH 9.0; 0.54 molar methionine sulfoxide (MSO)
in water, adjusted to pH 9.0; or 0.54 molar n-Dodecylamine (MAD) in
ethanol, adjusted to pH 9.0. In each case, 25 microliters each of DHA and
amine formulations are used on 25 cm.sup.2 of skin, readings are taken
after four hours of color development, water is allowed to flow over the
test sites for two minutes, and readings are taken again after patting dry
and air drying for thirty minutes.
Results are as follows:
______________________________________
% Color Color
Amine Remaining
Increase
______________________________________
Lysine 25.3 0.5
MSO 36.2 1.1
MAD 87.0 4.0
______________________________________
EXAMPLE 16
A test is conducted to demonstrate the more rapid color development
obtained when skin is treated with both DHA and amine. Two 25 cm.sup.2
areas are marked on the skin of two subjects. Both areas are treated with
25 microliters of the DHA formulation of preceding Example 5, and one of
the areas is additionally treated with 25 microliters of the amine
formulation of preceding Example 2. Values of .DELTA.E are determined at
hourly intervals for a period of seven hours. The results are as presented
below, wherein the data are derived from the equation
(.DELTA.E.sub.AMINE+DHA /.DELTA.E.sub.DHA):
______________________________________
Hours Subject 1
Subject 2
______________________________________
0 0 0
1 3.9 5.4
2 7.2 13.8
3 3.5 4.7
4 3.8 3.6
5 3.1 3.6
6 3.3 2.5
7 2.7 2.0
______________________________________
Although not shown in these data, the color is noticeably darker at each
measurement for the areas also treated with amine.
EXAMPLE 17
The following amines are incorporated into formulations, as with other
amines in the preceding examples, and applied to skin with DHA to provide
a simulated tan. Each amine has the general formula H.sub.2
N--(CH.sub.2).sub.x -Z, where x and Z are as indicated.
______________________________________
Amine x Z
______________________________________
2-(2-Aminoethoxy) ethanol
2 O(CH.sub.2).sub.2 OH
6-Amino-1-hexanol
6 OH
2,2-Diethoxyethylamine
1 CH(OCH.sub.2 CH.sub.3).sub.2
3-Aminopropyltriethoxy-
3 Si(OCH.sub.2 CH.sub.3).sub.3
silane
3-Aminopropyltrihydroxy-
3 Si(OH).sub.3
silane
8-Aminooctanoic acid
8 COOH
Furfurylamine 1 (C.sub.4 H.sub.3 O)
Tetrahydrofurfurylamine
1 (C.sub.4 H.sub.7 O)
Benzylamine 1 (C.sub.6 H.sub.5)
2-Aminoacetophenone
1 C(O) (C.sub.6 H.sub.5)
Triethyleneglycol diamine
2 (OCH.sub.2 CH.sub.2).sub.2 NH.sub.2
Tetraethyleneglycol diamine
2 (OCH.sub.2 CH.sub.2).sub.3 NH.sub.2
______________________________________
The invention has been described with respect to several specific
embodiments, but is not to be limited to those embodiments, the scope of
the invention being defined only by the appended claims. Various
improvements, alternatives and equivalents will be apparent to those
skilled in the art upon reading the foregoing description and examples,
and such are included within the claimed invention.
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